2 4 6-tris-(alkylthioalkylthio)-1 3 5-triazines

ABSTRACT

2,4,6-TRIS-(ALKYLTHIOALKYLTHIO)-1,3,5-TRIAZINES ARE PREPARED BY REACTING CYANURIC CHLORIDE, AND ALKYLTHIOALKYLMERCAPTAN AND A BASE. SAID COMPOUNDS ARE USEFUL AS STABILIZERS OF ORGANIC MATERIAL SUBJECT TO OXIDATIVE DETERIORATION AND PARTICULARLY AS SYNERGISTS IN COMBINATION WITH OTHER STABILIZERS.

United States atent Olfice Patented Mar. 28, 1972 US. Cl. 260-248 CS 9Claims ABSTRACT OF THE DISCLOSURE 2,4,6-tris(alkylthioalkylthio)-1,3,5-triazines are prepared by reacting cyanuricchloride, an alkylthioalkylmercaptan and a base. Said compounds areuseful as stabilizers of organic material subject to oxidativedeterioration and particularly as synergists in combination with otherstabilizers.

DETAILED DESCRIPTION This invention relates to2,4,6-tris-(alkylthioalkylthio)- 1,3,5-triazines and to organiccompositions otherwise subject to oxidative deterioration stabilized bythe incorporation therein of said types of compounds.

In particular the present invention pertains to the triazine compoundshaving the following general formula:

wherein R is alkyl group having up to 24 carbon atoms n is an integer of2 to 18.

By the group C,,H is meant a straight chain or a branched chain alkylenegroup having from 2 to 18 carbon atoms. The alkylene groups can beattached to the sulfur atoms either through carbons which are adjacentto each other or through any other two non-adjacent carbons.Illustrative examples of such groups are ethylene, propylene, butylene,hexylene, decene, dodecene, tetradecene, octadecene and the like. Thepreferred group are those having from 2 to 6 carbon atoms and the mostpreferred is ethylene.

The R group in the above formula is an alkyl group having from 6 to 24carbon atoms or an alkylthioalkane group, i.e., -C H S-R where theinteger in is l to 6 and R is an alkyl group having from 6 to 24 carbonatoms. Illustrative examples of the alkyl groups are hexyl, octyl,t-octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl,eicosyl, docosyl, tetracosyl and the like. Illustrative examples ofalkylthioalkyl groups are hexylthioethyl, octylthioethyl,dodecylthioethyl, tridecylthioethyl, octadecylthioethyl,tetracosylthioethyl, dodecylthiobutyl, octadecylthiobutyl,hexylthiohexyl and the like. The alkyl groups in R and R preferably havefrom 8 to 18 carbon atoms.

The 2,4,6-tris-(alkylthioalkylthio)-l,3,5-triazines of this inventioncan be prepared by a process comprising reacting cyanuric chloride, theappropriate mercaptan and a base in a solvent under an inert atmosphere.This process is described in greater detail in Examples 1 to 6 below.

The triazine compounds of the present invention are stabilizers oforganic material normally subject to oxidative deterioration. Materialswhich are thus stabilized according to the present invention includesynthetic organic polymeric substances such as vinyl resins formed fromthe polymerization of vinyl halides or from the copolymerization ofvinyl halides with unsaturated polymerrzable compounds, e.g., vinylesters, a,fl-unsaturated aldehydes and unsaturated hydrocarbons such asbutadienes and styrene, poly-a-olefins such as polyethylene,polypropylene, polybutylene, polyisoprene and the like, includingcopolymers of poly-a-olefins, polyurethanes such as are prepared frompolyols and organic polyisocyanates; polyamides such aspolyhexarnethylene adipamrde and polycaprolactam, polyesters such aspolymethylene or polyethylene terephthalates; polycarbonates;polyacetals; polystyrene; polyethyleneoxide; and copoly mers such asthose of high impact polystyrene containing copolymers of butadiene andstyrene andth'ose formed by the copolymerization of acrylonitrile,butadiene and/ or styrene. Other materials stabilized according to thepresent invention include lubrication oil of the aliphatic ester type,e.g., di(2-ethylhexyl)-azelate, pentaerythritol tetracaproate and thelike; animal and vegetable derived oils, e.g., linseed oil, fat, tallow,lard, peanut oil, cod liver oil, castor oil, palm oil, corn oil, cottonseed oil, and the like; hydrocarbon material such as gasoline, mineraloil, fuel oil, drying oil, cutting fluids, waxes, resins, and the like,fatty acids, soaps and the like.

lln general the stabilizers of this invention are employed from about0.005% to about 10% by Weight of the stabilized composition. Aparticularly advantageous range for polyolefins, such as polypropyleneis from about 0.1% to about 1%.

Although the compounds of this invention are useful as stabilizers perse, their greatest importance resides in the ability to vastly improvethe effectiveness of numerous other compounds especially phenoliccompounds, which are used as stabilizers for organic materials normallysubject to deterioration. Thus, the compounds of this invention may beclassified as synergists since when they are combined with stabilizersthey exhibit the ability to increase the total stabilization to a degreefar exceeding that which could be expected from the additive propertiesof the individual components. The stabilizers with which the compoundsof this invention may be combined are, generally, phenolic triazines,phenolic phosphonates, phenolic esters and phenolic hydrocarbons.

Typical of the phenolic antioxidants whose stabilizing properties areimproved by the addition of the compounds of the present invention, arethe following:

CLASS A.-PHENOLIC TRIAZINE STABILIZERS 6- (4'-hydroxy-3 -methyl-5-t-butylanilino) -2,4-bis noctylthio -1 ,3 ,5 -triazine 6- (4'-hydroxy-3',5 '-dimethylanilino) -2,4-bis (n-octylthio)-1,3,5-triazine 6-4'-hydroxy-3 ',5 -di-t-butylanilino -2,4-bis(n-octylthioethylthio 1 ,3,5 -triazine 2,4-bis- 4'-hydroxy-3 ',S'-di-t-butylphenoxy -6-n-octylthio 1 3 ,S-triazine 6- 4-hydroxy-3 ',5 '-di-t-butylanilino-2,4-bis (phenoxy 1,3 ,S-triazine 6- (4-hydroxy-3',5'-di-t-butylanilino)-4- (4-hydroxy-3 5"-di-t-butylphenoxy)-2- (n-octylthio)-1,3,5-triazine6- (4'-hydroxy-3 -t-butylphenoxy) -2,4-bis- (n-octylthioethylthio)-1,3,5-triazine 2,4,6-tris- (4'-hydroxy-3'-methyl-5'-t-butylphenoxy) 1,3,5 -triazine 2,4-bis-(4'-hydroxy-3,5-di-t-butylphenoxy -6-amino- 1,3,5-triazine 2,4-bis- (4-hydroxy-3',5'-di-t-butylphenoxy)-6-dodecylamino-1,3,5-triazine 6- (4'-hydroxy-3 ',5 -di-t-butylphenoxy)-2,4-b is (n-octylthiopropylthio)-1,3 ,5 -triazine 2,4-bis-(4'-hydroxy-3 ,5 -di-t-butylphenoxy) -6- (n-octadecylthio)-1,3,5-triazine 2,4-bis-(4'-hydroxy-3',5'-di-t-butylphenoxy)-6-(n-octylthiopropylthio)-1,3,5-triazine2,4-bis- (4'-hydroxy-3',5'-di-t-butylphenoxy)-6-(n-octy1- thioethylthio)1 ,3,5-triazine The above phenolic triazine stabilizers are more fullydescribed in U.S. Pat. No. 3,255,191.

CLASS B.PHENOLIC PHOSPHONATE STABILIZERS Among the many phosphonatestabilizers whose properties are improved by the addition of a compoundof the present invention are the di-(lower) alkyl phosphonates disclosedin U.S. Pat. No. 3,006,945. Particularly valuable phenolic phosphonatesin this regard however are the di- (higher)alkyl phenyl phosphonates,i.e., having from 14 to 30 carbon atoms in each alkyl group.Representative of these are the following:

Di-n-octadecyl 3-t-butyl-4-hydroxy-5-rneth ylbenzylphosphonateDi-n-octadecyl 1- 3 ',5 '-di-t-butyl-4-hydroxyphenyl ethanephosphonateDi-n-octadecyl 3,5-t-butyl-4-hydroxybenzylphosphonate The abovedi-(higher) alkyl phenolic phosphonates are more fully described in theapplication of John Spivack, Ser. No. 308,345, filed Sept. 12, 1963, nowabandoned.

CLASS C.--PHENOLIC ESTER STABILIZERS Subclass C-l n-Octadecyl3,5-di-t-butyl-4-hydroxyphenylacetate n-Octadecyl3,5-di-t-butyl-4-hydroxybenzoate Neo-dodecyl 3- (3 ',5-di-t-butyl-4'-hydroxyphenyl propionate Dodecyl 3- 3 ,5-di-t-butyl-4-hydroxyphenyl -propionate Ethyla-(4-hydroxy-3,S-di-t-butylphenyl)isobutyrate Subclass C-2 2-(n-octylthio -ethyl 3 ',5 '-di-t-butyl-4'-hydroxybenzoate 2-(n-octadecylthio ethyl 3 ,5 -di-t-butyl-4-hydroxyphenylacetate 2-(2-hydroxyethylthio) ethyl 3 ",5 "-di-t-butyl-4"-hydroxybenzoate[3,}3'-Thiodiethyl bis (3 ,5 -di-t-b utyl-4-hydroxyphenylacetate)Diethylene glycol bis- [3- 3 ',5 '-di-t-butyl-4'-hydroxyphenylpropionate] Thio-bis- [ethylene 3- 3 ',5 -di-t-butyl4'-hydroxyphenyl)propionate] Stearamido N,N-bis- [ethylene 3- 3 ',5-di-t-butyl-4'-hydroxyphenyl) propionate] n-Butylimino N,N-bis-[ethylene 3- 3 ,5 -di-t-butyl-4-hydroxyphenyl ropionate 2-2'-stearoyloxyethylthio ethyl 7- (3 "-methyl-S -t-butyl-4"-hydroxyphenyl heptanoate Subclass C-3 C-2, and C-3 are more fullydescribed in U.S. Pat. No. 3,330,859, Ser. No. 354,464, filed Mar. 24,1964, now U.S.

4 Pat. No. 3,441,575, and Ser. No. 359,460, filed Apr. 13, 1964, nowabandoned.

CLASS D.PHENOLIC HYDROCARBON STABILIZERS 4,4'-butylidene-bis6-t-butyl-m-cresol) 4,4thio-bis- 6-t-butyl-m-cresol) 4,4'-methylene-bis-2,6-di-t-butylphenol) 2,2-methylene-bis [4-hydroxy-6-(l-methylcyclohexyl) phenol] 1,3 ,5 -trimethyl-2,4,6-tris- 4'-hydroxy-3',5 '-di-tbutylbenzyl) benzene 2,6-di-t-butylphenol1,1,3-tris-(5'-t-butyl-4'-hydroxy-2'-methylphenyl)-butane4,4'-isopropylidene-bis- Z-t-butylphenol) The above phenolic hydrocarbonstabilizers are known and many are commercially available.

In addition to one or more of the above phenolic stabilizers, it isoften advantageous to employ other additives such as ultraviolet lightabsorbers, e.g., 2-hydroxy-4- methoxybenzophenone, 2 (2hydroxy-5'-methylphenyl) benztriazole, etc.; various phosphite compoundssuch as trioctyl phosphite, dilauryl phosphite, tris(nonylphenyl)phosphite and the like. Such two, three or four component systems, whenincluding a compound of the present invention, exhibit far superiorproperties to the additive properties of the individual components.

Other materials often added to such organic materials, depending uponthe substrate, include pourpoint depressants, corrosion and rustinhibitors, metal deactivators, dernulsifiers, 'antifoam agents, carbonblack, accelerators, plasticizers, color stabilizers, heat stabilizers,dyes, pigments and the like.

The above listed stabilizers may be used in the concentration of fromabout 0.005 to 10 percent by Weight of the stabilized composition. Aparticularly advantageous range is from about 0.1% to 1% by weight.

The following examples will further illustrate the nature of the presentinvention without being a limitation thereof.

EXAMPLE 1 Preparation of 2,4,6-tris-(n-octylthioethylthio) -1,3,5-triazine A reaction vessel Was charged with 9.2 g. of cyanuric chloridein ml. of ethanol and 30.9 g. of n-octylthioethyl mercaptan. The vesselwas flushed with nitrogen and cooled to 0 C. While stirring 3.45 g. ofsodium metal dissolved in 200 ml. of ethanol were added to the reactionmixture. About 30 minutes after the addition had been completed, thereaction mixture was allowed to warm to 20 C. and then flooded withwater. On standing and cooling the reaction product solidified and wasextracted with ether. The ether extract was dried over magnesiumsulfate, filtered and the ether stripped, yielding an almost colorlessviscous liquid weighing 31.3 g. This product was redissolved in ether,dried, filtered and stripped again, yielding 30.7 g. of viscous liquidwhich crystallized on standing. This material had a melting point of 32C.

Elemental analysis.-S, 27.7%. Found: S, 26.93%.

EXAMPLE 2 Preparation of 2,4,6-tris-(n-dodecylthioethylthio)-1,3,5-triazine To the reaction vessel were added 18.45 g. of cyanuricchloride dissolved in 200 ml. of acetone and 78.6 g. ofn-dodecylthioethyl mercaptan. The solution was cooled to 0 C. and to itwas added 23.1 g. of sodium hydroxide as a 51.9% solution over a periodof about 1 hour. The reaction mixture was allowed to Warm to roomtemperature and stirred for an additional hour. Then the mixture wasfiltered and washed several times with large amounts of water. Theexcess water was removed from the solid by suction and the solid wasdried over phosphoric anhydride. After drying the crude product weighed85.1 g.

and had a melting point of 52.5 to 55.0" C. The crude product wasdissolved in 1.4 liters of boiling isopropanol, cooled to about 50 C. atwhich time 375 ml. of hexane was added to prevent the separation of anoil. This solution was filtered and cooled slowly, yielding 64.8 g. ofthe product which had a melting point of 56-7 C.

Elemental analysis.Theory (percent): C, 62.78; H, 10.19; S, 22.35. Found(percent): C, 62.93; H, 9.93; S, 22.42.

Employing the procedure described above, 2,4,6-tris-(n-hexylthioethylthio)-1,3,5-triazine is prepared by substitutingn-hexylthioethylmercaptan in Example 2 above.

EXAMPLE 3 Preparation of 2,4,6-tris-(n-tetradecylthioethylthio)-1,3,5-

triazine Following the procedure described in Example 2 the product wasprepared by reacting 6.14 g. of cyanuric chloride, 29.0 g. ofn-tetradecylthioethylmercaptan and 4.0 g. of sodium hydroxide. Theproduct had a melting point of 63.5-64.5 C.

Elemental analysis.-Theory (percent): C, 64.70; H, 10.54; S, 20.32.Found (percent): C, 64.67; H, 10.57; S, 20.16.

EXAMPLE 4 EXAMPLE 5 Preparation of2,4,6-tris-(n-octylthioethylthioethyl)-1,3,5-

triazine Following the procedure described in Example 2, 3.68 g. ofcyanuric chloride, 16.00 g. of n-octylthioethylthioethylmercaptan and4.62 g. of sodium hydroxide were reacted in about 80 ml. of acetone togive the crude product. This product was recrystallized from hot hexaneyielding the purified product which has a melting point of 52-3 C.

Elemental analysis.-Calculated (percent) C, 53.55 H, 8.64; S, 33.00.Found (percent): C, 53.33; H, 8.43; S, 32.95.

EXAMPLE 6 Preparation of 2,4,6-tris-(tetracosylthioethylthioethylthio)1,3 ,5 -triazine The product is obtained by employing in Example 5,n-tetracosylthioethylthioethylmercaptan.

OVEN AGING TEST Unstabilized polypropylene powder (Hercules Profax 6501)is thoroughly blended with an antioxidant. The blended material is thenmilled on a two roller mill at 182 C. for minutes after which time thestabilized polypropylene is sheeted from the mill and allowed to cool.

The milled polypropylene sheet is then cut into small pieces and pressedfor 7 minutes on a hydraulic press at 218 C. and 2000 pounds per squareinch pressure. The resultant sheet of 25 mil thickness is cut into smallplaques and tested for resistance to accelerated aging in a forced draftoven at 150 C.

When unstabilized polypropylene is tested as described above, its ovenlife is about 3 hours.

The examples below show the effectiveness of the compounds of thisinvention as stabilizers per se, as well as the unusually highsynergistic activity of said compounds when employed in combination withother stabilizers.

Following is the control data showing the oven aging life ofpolypropylene stabilized with the indicated compounds. The compounds arealso used in combination with the compounds of this invention instabilizing various substrates as shown in Examples 7 to 18.

CONTROL Hrs. 0.1% Compound (A): Dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate 50 0.1% Compound (B):2,4-bis-(3,5-di-t-butyl-4'-hydroxyphenoxy)-6-(n-octylthio)-1,3,5-triazine 0.1% Compound (C):2,4-bis-(n-octylthio)-6-(3,5'-

di-t-butyl-4'-hydroxyanilino)-1,3,5-triazine 120 0.1% Compound (D):Tetra-[3-(3',5-di-t-butyl-4- hydroxyphenyl) propionyloxymethyl]methane600 EXAMPLE 7 Hrs. 0.5% 2,4,6-tris-(n-octylthioethylthio) 1,3,5 triazine35 0.1% Compound (A): 0.52,4,6-tris-(n-octylthioethylthio)-1,3,5-triazine 1960 0.1% Compound (C):0.5 2,4,6-tris-(n-octylthioethylthio)-1,3,5-triazine 1735 EXAMPLE 8 Hrs.0.5 2,4,6-tris-(n-tetradecylthioethylthio)-l,3,5-triazine 265 0.1%Compound (B): 2,4,6-tris-n(-tetradecylthioethylthio)-l,3,5-triazine 28100.25 Compound (B): 0.52,4,6-tris-(n-tetradecylthioethylthio)-1,3,5-triazine 3230 EXAMPLE 9Hrs. 0.5 2,4,6 tris (n-octadecylthioethylthio)-l,3,5-

triazine 30 0.1% Compound (B): 0.25%2,4,6-tris-(n-octadecylthioethylthio)-1,3,5-triazine 1020 0.1% Compound(B): 0.5% 2,4,6-tris-(n-octadecylthioethylthio)-1,3,5-triazine 17200.25% Compound (B): 0.25%2,4,6-tris-(n-octadecylthioethylthio)-1,3,5-triazine 1330 0.1% Compound(D): 0.5% 2,4,6-tris-(n-octadecylthioethylthio)-l,3,5-triazine 1330EXAMPLE 10 Hrs. 0.5 2,4,6 tris (n-octylthioethylthioethylthio)-1,3,5-triazine 0.1% Compound (B): 0.25%2,4,6-tris-(n-octylthioethylthioethylthio)1,3,5-triazine 1930 0.1%Compound (B): 0.5%2,4,6-tris-(n-octylthioethylthioethylthio)-1,3,5-triazine 2510 EXAMPLE11 Hrs. 0.5 2,4,6 tris (n-dodecylthioethylthio) 1,3,5-

triazine 0.1% Compound (B): 0.5% 2,4,'6-tris(n-dodecylthioethylthio)-1,3,5-triazine 2570 0.1% Compound (B): 0.25%2,4,6-tris-(n-dodecylthioethylthio)-1,3,5-triazine 2190 Besidespolypropylene, the above combinations of stabilizers are also effectivewhen employed with polyethylene, polysytrene, polyurethane,polyvinylchloride, styrene-butadiene-acrylonitrile copolymer andpolyamides.

In addition to the combinations of stabilizers shown above, thefollowing combinations also exhibit excellent stabilization ofpolypropylene:

(a) v6-(4'-hydroxy-3'-metl1yl-5'-t-buty1anilino)-2,4-bis-(n-octylthio)-l,3,5-triazine and 2,4,6-tris-(hexylthioethylthio)-1,3,5-triazine (b) 2,4-bis (n-octylthio -6-3,5 ',di-t-butyl-4'-hydroxyanilino)-1,3,5-triazine and2,4,6-tris-(n-tetracosylthioethylthio 1 3 S-triazine (c) n-Octadecyl3-(3,5',-di-t-butyl-4'-hydroxyphenyl) propionate and2,4,6-tris-(n-eicosylthioethylthio)-1,3,5-triazine (d) Di-n-octadecyl3,5-di-t-butyl-4-hydroxybenzylphosphonate and2,4,6-tris-(n-octadecylthioisopropylthio) l ,3,5triazine (e)2,4-bis(4'-hydroxy-3',5'-di-t-butylphenoxy)-6-(n-octylthioethylthio)-1,3,5-triazine and 2,4,6- tris-(n-octadecylthiobutylthio -1, 3 5-triazine (f)Tetrakis-[3-(3',5-di-t-butyl-4'-hydroxphenyl) propionyloxymethyl]methane and 2,4,6-tris- (noctadecylthiohexylthio -1, 3 S-triazine (g)1,1, l-tris- [3 3 ",5"-di-t-butyl-4"-hydroxyphenyl)propionyloxymethyl]-propane and2,4,6-tris- (n-hexylthioethylthioethylthio -1, 3 S-triazine (h)Di-n-octadecyl 1-(3",5"-di-t-butyl-4"-hydroxyphenyl)-ethanephosphonateand 2,4,6-tris-(n-tetracosylthiohexylthiohexylthio -1, 3 ,5 -triazine(i) 1,2-propylene glycol bis-[3'-(3",5"-di-t-butyl-4"-hydroxyphenyl)propionate and2,4,6-tris(n-octadecylthiobutylthiobutylthio)-1,3,5-triazine (j)4,4-butylidene-bis(6-t-butyl-m-cresol) and 2,4,6-

tris- (n-tetracosylthioethylthioethylthio 1, 3 5 -triazine EXAMPLE 12 Astabilized mineral oil composition is prepared by incorporating into arefined mineral oil of 183 S.U.S. at 100 F. (Regal Oil B, Texas Company)0.005% by weight of 2,4,6-tris-(n-octylthioethylthio) 1,3,5 triazine.Even better stabilization is obtained when in combination with saidtriazine compound is used 6-(4-hydroxy-3',5'-di-tbutylani1ino)-2,4bis(phenoxy)-1, 3 S-triaZine.

EXAMPLE 13 Stabilized lard is prepared by incorporating in lard 0.01% byWeight of 2,4,6-tris- (n-tetradecylthioethylthio)- 1,3,5-triazine.

Stabilized cotton seed oil is prepared when 0.01% by weight of thisstabilizer is incorporated in a refined cotton seed oil.

EXAMPLE l4 Stabilized gasoline is prepared by incorporating intogasoline having no additives and no stabilizers therein, 0.05% by weightof 2,4,6-tris-(n-octadecylthioethylthio)- 1,3,5-triazine. Stabilizationis further improved by the addition of 0.02% by weight of2,4-bis-(4'-hydroxy-3',5- di t butylphenoxy)-6- (ndodecylthioethylthio)-1,3,5- triazine.

EXAMPLE 15 Parafiin was (M.P. 125-128 F.) is stabilized by incorporatingtherein 0.001% by weight of2,4,6-tris-(octylthioethylthioethylthio)-1,3,5-triazine. An improvedstabilization is obtained when additionally 0.005% by weight ofdi-n-tetradecyl 3,5-di-t-butyl 4 hydroxybenzyl-phosphonate is added.

EXAMPLE 16 A stabilized high temperature lubrication oil is prepared byincorporating 2% by weight of2,4,6-tris-(ndodecylthioethylthio)-1,3,5-triazine into lubricant, whichcomprises diisoarnyladipate. The stabilization of said lubricant isfurther improved by the addition of diethylene glycol bis- 3- (3 '5'-di-t-butyl-4'-hydroxyphenyl) propionate].

EXAMPLE 17 High impact polystyrene resin containing elastomer (i.e.,butadiene-styrene) is stabilized against loss of elongation propertiesby incorporation of 0.5% by weight of 2,4,6 tris(n-dodecylthioethylthioethylthio) 1,3,5-triazine and 1.0% by weight oftetrakis-[3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionyloxymet-hyl)]-methane.

Similar results are obtained with terpolymer ofacrylonitrile-butadiene-styrene.

EXAMPLE 18 A polyethylene composition is prepared by adding topolyethylene 0.2% by Weight of carbon black, 0.3% by weight of2,4,6-tris-(n-octadecylthioethylthioethylthio)- 1,3,5-triazine and 0.1%by weight of dioctadecyl 3,5-dit-butyl-4-hydroxybenzylphosphonate. Thethus stabilized polyethylene exhibits much more stability thanpolyethylene containing only carbon black or carbon black with saidphenolic stabilizer.

What is claimed is:

1. A triazine compound having the formula:

wherein R is alkyl group having from 6 to 24 carbon atoms or --C H S-R',where m is from 2 to 6 and R is alkyl group having from 6 to 24 carbonatoms, and n is an integer from 2 to 18.

2. A compound according to claim 1 wherein n is from 2 to 6.

3. A compound according to claim 1 wherein n is 2 and R is alkyl grouphaving from 6 to 18 carbon atoms.

4. A compound according to claim 1 wherein n is from 2 to 6 and R is C HS-R where m is 2 and R is alkyl group having from 6 to 18 carbon atoms.

5. A compound according to claim 1 wherein said triazine compound is2,4,6-tris-(n-octylthioethylthio)-1,3,5- triazine.

6. A compound according to claim 1 wherein said triazine compound is2,4,6-tris-(n-dodecylthioethylthio)- 1,3,5-triazine.

7. A compound according to claim 1 wherein said triazine compound is2,4,6-tris-(n-tetradecylthioethylthio)- 1,3,5-triazine.

8. A compound according to claim 1 wherein said triazine compound is2,4,6-tris-(n-octadecylthioethylthio)- 1,3,5-triazine.

9. A compound according to claim 1 wherein said triazine compound is2,4,6-tris(n-octylthioethylthioethylthio)-1,3,5-triazine.

References Cited UNITED STATES PATENTS 3,245,992 4/1966 Dexter et a1.260248 JOHN M. FORD, Primary Examiner US. Cl. X.R.

